Crystal structure and theoretical study of (2E)-1-[4-hy-droxy-3-(morpholin-4-ylmeth-yl)phen-yl]-3-(thio-phen-2-yl)prop-2-en-1-one.

In the title compound, C18H19NO3S, the morpholine ring adopts a chair conformation. The thio-phene ring forms dihedral angles of 26.04 (9) and 74.07 (10)° with the benzene ring and the mean plane of the morpholine ring, respectively. The mol-ecular conformation is stabilized by an O-H⋯N hydrogen bond. In the crystal, mol-ecules are connected through C-H⋯O hydrogen bonds, forming wave-like layers parallel to the ab plane, which are further linked into a three-dimensional network by C-H⋯π inter-actions involving the benzene rings and the methyl-ene H atoms of the morpholine rings.

Chemical context

Chalcones, viz 1,3-diaryl-2-propene-1-ones, are major component of many natural products as well as important precursors for many synthetic manipulations (Das et al., 2006 ▸; Yerdelen et al., 2015 ▸; Gul et al., 2009 ▸). Chalcones and their synthetic analogues display a wide range of biological activities such as anti­cancer, anti­malarial, anti­bacterial, anti-inflammatory, anti­fungal, anti­oxidant, anti-HIV, anti­protozoal, and carbonic anhydrase inhibiting activities (Das et al., 2006 ▸; Yerdelen et al., 2015 ▸; Gul et al., 2007 ▸, 2009 ▸; Bilginer et al., 2013 ▸, 2014 ▸; Yamali et al., 2016 ▸; Singh et al., 2014 ▸).

Mannich bases are an important class of compounds in medicinal chemistry. The Mannich reaction can be considered as a substitution reaction of a suitable compound in which one or more amino­methyl­ation processes happen, depending on the nature of the reactants. The biological activities of Mannich bases may result from their chemical structures or from the production of α,β-unsaturated ketone moieties (Roman, 2015 ▸). The title compound was designed with the expectation of observing an increased bioactivity or cytotoxicity in a mol­ecule including both chalcone and Mannich base pharmakophores.

Structural commentary

In the title compound (Fig. 1 ▸), the morpholine ring (N1/O3/C15–C18) adopts a chair conformation with puckering parameters Q T = 0.5776 (18) Å, θ = 0.00 (19)°, φ = 308 (12)°. The benzene ring (C8–C13) forms dihedral angles of 26.04 (9) and 79.95 (8)° with the thio­phene ring (S1/C1–C4) and the mean plane of the morpholine ring, respectively. The values of all bond lengths and angles in the title compound are unexceptional. The mol­ecular conformation is enforced by an intra­molecular O—H⋯N hydrogen bond (Table 1 ▸).

Figure 1

The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C8–C13 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O⋯N1	0.83 (2)	1.94 (2)	2.6834 (18)	149 (3)
C1—H1⋯O1i	0.93	2.38	3.249 (2)	156
C2—H2⋯O2ii	0.93	2.57	3.417 (2)	152
C16—H16A⋯Cg1iii	0.97	2.88	3.789 (2)	157
C18—H18B⋯Cg1iv	0.97	2.70	3.6010 (18)	154

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Supra­molecular features

In the crystal, mol­ecules are linked by inter­molecular C—H⋯O hydrogen bonds, forming wave-like layers parallel to the ab plane (Table 1 ▸, Fig. 2 ▸). C—H⋯π inter­actions are observed between the benzene rings and the methyl­ene hydrogen atoms of the morpholine rings in adjacent layers, forming a three-dimensional network.

Figure 2

The mol­ecular packing of the title compound viewed down the a axis. Hydrogen bonds are shown as dashed lines.

Database survey

A search of the Cambridge Structural Database (Version 5.39, update May 2018; Groom et al., 2016 ▸) for the 2-(morph­olino­meth­yl)phenol substructure yielded two hits, namely BOPMEY (Fun et al., 1999 ▸) and IHUBIW (Xie et al., 2003 ▸). In both compounds, the amine N atoms of the morpholine rings and the hy­droxy groups of the phenol fragments are engaged in intra­molecular hydrogen bonds.

Theoretical calculations

A quantum-chemical calculation was performed using the CNDO (Complete Neglect of Differential Overlap; Pople & Beveridge, 1970 ▸) approximation. A view of the calculated mol­ecule is shown in Fig. 3 ▸. The charges at atoms S1, O1, O2, O3 and N1 are −0.049, −0.336, −0.271, −0.224 and −0.145 e−, respectively. The calculated dipole moment of the title mol­ecule is ca 2.881 Debye. The HOMO and LUMO energy levels are −10.3681 and 1.4009 eV, respectively.

Figure 3

Spatial view of the title compound calculated using the CNDO method.

In addition, the geometrical optimization calculations of the title compound were performed using the PM3 (Parameterized Model number 3) method (Stewart, 1989 ▸) in WinMopac7.2. A view of the mol­ecule calculated with PM3 is shown in Fig. 4 ▸. The net charges at atoms S1, O1, O2, O3 and N1 are 0.321, −0.230, −0.260, −0.321 and −0.070 e−, respectively. The calculated dipole moment of the title mol­ecule is ca 1.176 Debye. The HOMO and LUMO energy levels are −0.1724 and 0.0829 eV, respectively. These calculations were performed assuming the mol­ecule to be isolated and in an absolute vacuum. A comparison between experimental and calculated bond lengths (r.m.s. deviations of 0.029 and 0.016 Å for CNDO and PM3, respectively) and angles (r.m.s. deviations of 1.601 and 1.915° for CNDO and PM3, respectively) is given in Table 2 ▸. The PM3 method gave the lowest values for HOMO, LUMO and dipole moments.

Figure 4

Spatial view of the title compound calculated using the PM3 method

Table 2

Comparison of experimental (X-ray), theoretical (CNDO and PM3) parameters (Å, °) of the title compound

Bond/Angle	X-ray	CNDO	PM3
S1—C1	1.705 (2)	1.7663	1.7194
S1—C4	1.720 (2)	1.7758	1.7449
O1—C7	1.224 (2)	1.2143	1.2196
O2—C11	1.354 (2)	1.3565	1.3663
O3—C16	1.419 (2)	1.4208	1.4149
O3—C17	1.422 (2)	1.4209	1.4153
N1—C14	1.472 (2)	1.4606	1.4916
N1—C15	1.469 (2)	1.4573	1.4914
N1—C18	1.469 (2)	1.4567	1.4906
C1—S1—C4	92.20 (9)	88.91	91.38
C16—O3—C17	109.29 (13)	110.44	112.79
C14—N1—C15	111.86 (13)	111.15	112.06
C14—N1—C18	110.61 (13)	111.92	112.86
C15—N1—C18	109.09 (13)	109.64	111.62
S1—C1—C2	111.75 (15)	111.11	112.58
S1—C4—C5	123.58 (12)	126.03	125.76
S1—C4—C3	109.79 (12)	109.88	111.11
O1—C7—C6	120.42 (14)	119.03	122.82
O1—C7—C8	119.90 (14)	123.49	121.52
O2—C11—C10	118.59 (14)	119.87	115.22
O2—C11—C12	121.18 (14)	122.06	123.98
N1—C14—C12	112.14 (12)	112.35	111.21
N1—C15—C16	109.98 (14)	110.79	109.89
O3—C16—C15	111.42 (17)	109.89	112.44
O3—C17—C18	111.22 (14)	110.05	112.30
N1—C18—C17	109.80 (15)	110.73	110.02

Synthesis and crystallization

A mixture of paraformaldehyde (0.13 g, 4.3 mmol) and morpholine (0.37 g, 4.3 mmol) in aceto­nitrile (5 ml) was refluxed at 353 K for 30 min. A solution of a suitable chalcone in aceto­nitrile (25 ml), [1-(4-hy­droxy­phen­yl)-3-(thio­phene-2-yl)-2-propene-1-one (1 g, 4.3 mmol)], was added into the reaction flask under continuous heating. The reaction progress was monitored by TLC. The reaction stopped after 8 h when the chalcone compound was consumed in the reaction medium, and the solvent was removed under vacuum. The residue was purified by column chromotography (SiO2; CHCl3: MeOH 9:1 v/v). Yield 32%, m.p. 424–426 K. Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. C-bound H atoms were placed in calculated positions with C—H = 0.93–0.97 Å and refined using a riding model with U iso(H) = 1.2U eq(C). The hy­droxy H atom was found in a difference-Fourier map and refined with U iso(H) = 1.5U eq(O). 15 outliers (5 4 6, 14 1, 5 3 2, 3 4 2, 3 1, 16 4, 11 1, 7 9, 11 1, 2 2 10, 0 5 12, 13 1, 13 3, 0 15 4, 17 4) were omitted in the final cycles of refinement.

Table 3

Experimental details

Crystal data
Chemical formula	C18H19NO3S
M r	329.40
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	293
a, b, c (Å)	9.4939 (5), 18.5548 (10), 9.5068 (5)
β (°)	96.788 (3)
V (Å3)	1662.95 (15)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.21
Crystal size (mm)	0.81 × 0.50 × 0.48
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 ▸)
T min, T max	0.882, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	33902, 4168, 3373
R int	0.033
(sin θ/λ)max (Å−1)	0.670
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.050, 0.138, 1.03
No. of reflections	4168
No. of parameters	211
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.32, −0.25

Computer programs: APEX2 and SAINT (Bruker, 2007 ▸), SHELXS2014 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2008 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018008459/rz5238sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018008459/rz5238Isup4.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018008459/rz5238Isup3.cml

CCDC reference: 1848116

Additional supporting information: crystallographic information; 3D view; checkCIF report

C18H19NO3S	F(000) = 696
Mr = 329.40	Dx = 1.316 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4939 (5) Å	Cell parameters from 9868 reflections
b = 18.5548 (10) Å	θ = 2.2–28.4°
c = 9.5068 (5) Å	µ = 0.21 mm−1
β = 96.788 (3)°	T = 293 K
V = 1662.95 (15) Å3	Prism, colourless
Z = 4	0.81 × 0.50 × 0.48 mm

Bruker APEXII CCD diffractometer	4168 independent reflections
Radiation source: sealed tube	3373 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 28.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −12→12
Tmin = 0.882, Tmax = 0.905	k = −24→24
33902 measured reflections	l = −12→12

Refinement on F2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.138	w = 1/[σ2(Fo2) + (0.0679P)2 + 0.4859P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4168 reflections	Δρmax = 0.32 e Å−3
211 parameters	Δρmin = −0.25 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
C1	0.3316 (2)	−0.02309 (12)	0.2121 (3)	0.0720 (6)
H1	0.235465	−0.019863	0.221873	0.086*
C2	0.3860 (2)	−0.06817 (11)	0.1231 (2)	0.0623 (5)
H2	0.331381	−0.099790	0.063433	0.075*
C3	0.53423 (18)	−0.06285 (9)	0.12897 (19)	0.0522 (4)
H3	0.587701	−0.090438	0.073164	0.063*
C4	0.59198 (16)	−0.01301 (8)	0.22504 (17)	0.0441 (3)
C5	0.74016 (16)	0.00373 (8)	0.25820 (17)	0.0447 (3)
H5	0.802258	−0.022598	0.209531	0.054*
C6	0.79903 (17)	0.05204 (9)	0.34953 (18)	0.0465 (4)
H6	0.741687	0.080254	0.400249	0.056*
C7	0.95402 (16)	0.06168 (8)	0.37183 (17)	0.0433 (3)
C8	1.01520 (15)	0.12698 (8)	0.44638 (15)	0.0398 (3)
C9	0.93436 (16)	0.18710 (8)	0.47309 (16)	0.0435 (3)
H9	0.836671	0.186378	0.448048	0.052*
C10	0.99807 (17)	0.24766 (8)	0.53638 (17)	0.0456 (3)
H10	0.943157	0.287658	0.552522	0.055*
C11	1.14360 (16)	0.24932 (8)	0.57615 (15)	0.0410 (3)
C12	1.22777 (15)	0.18990 (8)	0.54966 (15)	0.0390 (3)
C13	1.16227 (15)	0.13017 (8)	0.48509 (15)	0.0397 (3)
H13	1.217489	0.090658	0.466589	0.048*
C14	1.38542 (17)	0.19118 (9)	0.59817 (18)	0.0473 (4)
H14A	1.401057	0.181264	0.698985	0.057*
H14B	1.431423	0.153440	0.549728	0.057*
C15	1.45567 (19)	0.27260 (10)	0.41787 (17)	0.0533 (4)
H15A	1.360309	0.272216	0.368303	0.064*
H15B	1.508851	0.233930	0.380183	0.064*
C16	1.5255 (2)	0.34382 (12)	0.3944 (2)	0.0645 (5)
H16A	1.529884	0.350654	0.293866	0.077*
H16B	1.468902	0.382512	0.427116	0.077*
C17	1.65806 (19)	0.33755 (12)	0.6150 (2)	0.0603 (5)
H17A	1.601485	0.375827	0.649325	0.072*
H17B	1.752902	0.340669	0.665265	0.072*
C18	1.59421 (16)	0.26603 (10)	0.64480 (18)	0.0507 (4)
H18A	1.652343	0.227514	0.613763	0.061*
H18B	1.591062	0.260745	0.745894	0.061*
N1	1.45003 (13)	0.26102 (7)	0.56999 (13)	0.0425 (3)
O1	1.03248 (13)	0.01683 (7)	0.32762 (15)	0.0605 (3)
O2	1.20139 (14)	0.30917 (7)	0.64087 (14)	0.0548 (3)
O3	1.66467 (14)	0.34704 (8)	0.46745 (15)	0.0686 (4)
S1	0.45988 (5)	0.02779 (3)	0.30547 (7)	0.0781 (2)
H1O	1.2875 (19)	0.3090 (18)	0.633 (3)	0.117*

	U11	U22	U33	U12	U13	U23
C1	0.0407 (9)	0.0815 (14)	0.0932 (15)	0.0020 (9)	0.0062 (9)	−0.0139 (12)
C2	0.0505 (10)	0.0600 (11)	0.0743 (13)	−0.0078 (8)	−0.0017 (9)	−0.0083 (9)
C3	0.0508 (9)	0.0475 (9)	0.0585 (10)	0.0007 (7)	0.0072 (7)	−0.0053 (7)
C4	0.0416 (8)	0.0406 (8)	0.0499 (8)	0.0049 (6)	0.0046 (6)	0.0006 (6)
C5	0.0417 (8)	0.0414 (7)	0.0515 (8)	0.0031 (6)	0.0073 (6)	0.0028 (6)
C6	0.0419 (8)	0.0443 (8)	0.0538 (9)	0.0012 (6)	0.0084 (7)	−0.0019 (7)
C7	0.0426 (8)	0.0413 (8)	0.0470 (8)	−0.0013 (6)	0.0094 (6)	0.0031 (6)
C8	0.0394 (7)	0.0408 (7)	0.0405 (7)	−0.0009 (6)	0.0098 (6)	0.0044 (6)
C9	0.0370 (7)	0.0476 (8)	0.0472 (8)	0.0017 (6)	0.0102 (6)	0.0029 (6)
C10	0.0451 (8)	0.0430 (8)	0.0505 (9)	0.0060 (6)	0.0132 (7)	−0.0018 (6)
C11	0.0468 (8)	0.0414 (7)	0.0359 (7)	−0.0002 (6)	0.0086 (6)	0.0015 (6)
C12	0.0388 (7)	0.0417 (7)	0.0367 (7)	0.0007 (6)	0.0052 (6)	0.0066 (6)
C13	0.0401 (7)	0.0372 (7)	0.0427 (7)	0.0034 (6)	0.0090 (6)	0.0049 (6)
C14	0.0427 (8)	0.0468 (8)	0.0509 (9)	0.0011 (6)	−0.0012 (6)	0.0040 (7)
C15	0.0532 (9)	0.0672 (11)	0.0389 (8)	−0.0119 (8)	0.0035 (7)	−0.0032 (7)
C16	0.0651 (11)	0.0769 (13)	0.0532 (10)	−0.0191 (10)	0.0138 (8)	0.0029 (9)
C17	0.0433 (9)	0.0802 (13)	0.0587 (10)	−0.0145 (8)	0.0114 (7)	−0.0211 (9)
C18	0.0379 (8)	0.0673 (11)	0.0461 (8)	0.0016 (7)	0.0016 (6)	−0.0121 (7)
N1	0.0376 (6)	0.0507 (7)	0.0388 (6)	−0.0043 (5)	0.0032 (5)	−0.0020 (5)
O1	0.0456 (6)	0.0539 (7)	0.0837 (9)	0.0002 (5)	0.0151 (6)	−0.0174 (6)
O2	0.0554 (7)	0.0482 (6)	0.0605 (7)	−0.0024 (5)	0.0059 (6)	−0.0127 (5)
O3	0.0540 (7)	0.0911 (10)	0.0646 (8)	−0.0251 (7)	0.0234 (6)	−0.0133 (7)
S1	0.0495 (3)	0.0889 (4)	0.0965 (4)	0.0074 (2)	0.0111 (3)	−0.0427 (3)

C1—C2	1.336 (3)	C11—C12	1.402 (2)
C1—S1	1.705 (2)	C12—C13	1.379 (2)
C1—H1	0.9300	C12—C14	1.513 (2)
C2—C3	1.406 (2)	C13—H13	0.9300
C2—H2	0.9300	C14—N1	1.472 (2)
C3—C4	1.368 (2)	C14—H14A	0.9700
C3—H3	0.9300	C14—H14B	0.9700
C4—C5	1.439 (2)	C15—N1	1.469 (2)
C4—S1	1.7197 (16)	C15—C16	1.507 (3)
C5—C6	1.325 (2)	C15—H15A	0.9700
C5—H5	0.9300	C15—H15B	0.9700
C6—C7	1.473 (2)	C16—O3	1.419 (2)
C6—H6	0.9300	C16—H16A	0.9700
C7—O1	1.2239 (19)	C16—H16B	0.9700
C7—C8	1.487 (2)	C17—O3	1.422 (2)
C8—C9	1.394 (2)	C17—C18	1.500 (3)
C8—C13	1.403 (2)	C17—H17A	0.9700
C9—C10	1.380 (2)	C17—H17B	0.9700
C9—H9	0.9300	C18—N1	1.4691 (19)
C10—C11	1.389 (2)	C18—H18A	0.9700
C10—H10	0.9300	C18—H18B	0.9700
C11—O2	1.3538 (19)	O2—H1O	0.830 (18)
C2—C1—S1	111.75 (15)	C8—C13—H13	118.9
C2—C1—H1	124.1	N1—C14—C12	112.14 (12)
S1—C1—H1	124.1	N1—C14—H14A	109.2
C1—C2—C3	113.02 (18)	C12—C14—H14A	109.2
C1—C2—H2	123.5	N1—C14—H14B	109.2
C3—C2—H2	123.5	C12—C14—H14B	109.2
C4—C3—C2	113.24 (16)	H14A—C14—H14B	107.9
C4—C3—H3	123.4	N1—C15—C16	109.98 (14)
C2—C3—H3	123.4	N1—C15—H15A	109.7
C3—C4—C5	126.63 (15)	C16—C15—H15A	109.7
C3—C4—S1	109.79 (12)	N1—C15—H15B	109.7
C5—C4—S1	123.58 (12)	C16—C15—H15B	109.7
C6—C5—C4	127.99 (15)	H15A—C15—H15B	108.2
C6—C5—H5	116.0	O3—C16—C15	111.42 (17)
C4—C5—H5	116.0	O3—C16—H16A	109.3
C5—C6—C7	120.90 (15)	C15—C16—H16A	109.3
C5—C6—H6	119.6	O3—C16—H16B	109.3
C7—C6—H6	119.6	C15—C16—H16B	109.3
O1—C7—C6	120.42 (14)	H16A—C16—H16B	108.0
O1—C7—C8	119.90 (14)	O3—C17—C18	111.22 (14)
C6—C7—C8	119.67 (13)	O3—C17—H17A	109.4
C9—C8—C13	118.09 (14)	C18—C17—H17A	109.4
C9—C8—C7	123.12 (14)	O3—C17—H17B	109.4
C13—C8—C7	118.69 (13)	C18—C17—H17B	109.4
C10—C9—C8	120.57 (14)	H17A—C17—H17B	108.0
C10—C9—H9	119.7	N1—C18—C17	109.80 (15)
C8—C9—H9	119.7	N1—C18—H18A	109.7
C9—C10—C11	120.48 (14)	C17—C18—H18A	109.7
C9—C10—H10	119.8	N1—C18—H18B	109.7
C11—C10—H10	119.8	C17—C18—H18B	109.7
O2—C11—C10	118.59 (14)	H18A—C18—H18B	108.2
O2—C11—C12	121.18 (14)	C18—N1—C15	109.09 (13)
C10—C11—C12	120.23 (14)	C18—N1—C14	110.61 (13)
C13—C12—C11	118.39 (13)	C15—N1—C14	111.86 (13)
C13—C12—C14	121.74 (13)	C11—O2—H1O	108 (2)
C11—C12—C14	119.80 (13)	C16—O3—C17	109.29 (13)
C12—C13—C8	122.22 (13)	C1—S1—C4	92.20 (9)
C12—C13—H13	118.9
S1—C1—C2—C3	0.3 (3)	C10—C11—C12—C14	−177.78 (14)
C1—C2—C3—C4	0.4 (3)	C11—C12—C13—C8	−0.4 (2)
C2—C3—C4—C5	178.40 (16)	C14—C12—C13—C8	176.60 (13)
C2—C3—C4—S1	−0.9 (2)	C9—C8—C13—C12	0.9 (2)
C3—C4—C5—C6	179.33 (18)	C7—C8—C13—C12	177.50 (13)
S1—C4—C5—C6	−1.5 (3)	C13—C12—C14—N1	140.07 (14)
C4—C5—C6—C7	179.26 (15)	C11—C12—C14—N1	−42.94 (19)
C5—C6—C7—O1	−13.9 (3)	N1—C15—C16—O3	58.3 (2)
C5—C6—C7—C8	165.08 (15)	O3—C17—C18—N1	−59.52 (19)
O1—C7—C8—C9	166.04 (15)	C17—C18—N1—C15	56.66 (17)
C6—C7—C8—C9	−12.9 (2)	C17—C18—N1—C14	−179.90 (13)
O1—C7—C8—C13	−10.4 (2)	C16—C15—N1—C18	−55.98 (19)
C6—C7—C8—C13	170.68 (14)	C16—C15—N1—C14	−178.68 (15)
C13—C8—C9—C10	−0.3 (2)	C12—C14—N1—C18	167.76 (13)
C7—C8—C9—C10	−176.70 (14)	C12—C14—N1—C15	−70.41 (17)
C8—C9—C10—C11	−0.8 (2)	C15—C16—O3—C17	−59.5 (2)
C9—C10—C11—O2	−178.50 (14)	C18—C17—O3—C16	60.1 (2)
C9—C10—C11—C12	1.3 (2)	C2—C1—S1—C4	−0.7 (2)
O2—C11—C12—C13	179.13 (13)	C3—C4—S1—C1	0.90 (15)
C10—C11—C12—C13	−0.7 (2)	C5—C4—S1—C1	−178.40 (16)
O2—C11—C12—C14	2.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O···N1	0.83 (2)	1.94 (2)	2.6834 (18)	149 (3)
C1—H1···O1i	0.93	2.38	3.249 (2)	156
C2—H2···O2ii	0.93	2.57	3.417 (2)	152
C5—H5···O1	0.93	2.45	2.786 (2)	101
C16—H16A···Cg1iii	0.97	2.88	3.789 (2)	157
C18—H18B···Cg1iv	0.97	2.70	3.6010 (18)	154